Lubricating oil



R. S. VOSE LUBRICATING OIL Filed July 17, 1935 Patented ug. 15, 1939 LUBRICATING E Richard S. Vose, Ridley Park, Pa., assigner to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey Application .luly 17, 1935, Serial No. 31,824

9 Claims.

My invention relates to improved lubricating oils having a combination of qualities, comprising improved color, low organic acidity, good demulsibility, and particularly low Conradson carbon content and low Sligh oxidation numbers. These oils are preferably produced by specially treating distilled'lubricating oils with metallic sodium, or by specially treating a residuum, or mazoot, withmetallic sodium and then, by controlled methods such as, for example, as disclosed in Pew Patent No. 1,761,153, distilling my improved oils from the sodium treated mazoot. The herein described processes oi producing my improved oils, which are described and claimed in Patent No. 2,055,210, issued September 22, 1936, on my co-pending application Serial No. 685,994, iiled August 21, 1933, and of which this applicationis a continuation in part, are applicable to the treatment of any lubricating oils. The residual oil from which my improved lubricating oil distillates are distilled is believed to have a novel combination of qualities irrespective of the nature ofthe crude oil. It is particularly advantageous, however, to apply the processes to the treatment of naphthenic base oils (by which I mean to include mixed base oils), since when a residual oil of such a base is treated by such processes for the purpose of eiecting a substantial dehydrogenation of the unsaturates, it changes their temperatureviscosity characteristics to approximate those of a paraine base distillate, besides imparting to them a combination of qualities (including high fire and flash points, a negligible organic acidity denitive of an absolutely neutral oil, an excellent color, a verylow Conradson carbon content and a zero Sligh oxidation test) which have never heretofore characterized distillates derived from crude oil of such a base. I herein claim said residual oil broadly as well as applied to naphthenic base oils as above defined, and claim specifically the novel range of distillates derived from naphthenic base oils. l

It will be understood, also, that my invention is not limited to lubricating oils produced by the herein described process, nor necessarily to lubricating oils produced by treatment of the oils, or of the stock (residuum or mazoot) used to produce them, with metallic sodium, but said processes are herein fully described in order that those skilled in the art may have full and exact knowledge of practicable methods whereby they can be produced without the necessity of experiment.

The use of metallic sodium for the purpose of improving the qualities of, and particularly for desulphurizing,u gasoline is old and well known.

. The amount of sodium required for such purpose is so small as not to involve a prohibitive expense'. But it is impossible to treat lubricating oil with metallic sodium in an amount at all comparable with that required for the treatment of gasoline and secure any substantial improvement in the quality of the oil. It is known, however, to treat naphthenic base lubricating oil with metallic sodium in much greater amounts and substantially improve some of its qualities, but the main objects of my invention, particularly delrvdrogenation of unsaturates and change of temperature-viscosity relationship to approximate that characteristic of paramne base lubricating oils, have not been achieved.

The preferred process for treating lubricating oil distillates, or oil containing lubricating oil fractions before distillation of the lubricating oils, involves the use of a comparatively large amount of metallic sodium at a temperature above its melting point. It involves, also, the formation by the sodium of a colloidal or quasi-colloidal suspension in the oil to give a maximum ratio of contact surface to weights of sodium. The process also involves a method for securing a nearly quantitative recovery of the sodium, Without which the process is uneconomical.

Briefly, the process consists in mixing oil with the proper amount of sodium, at a temperature above the melting point of the sodium, and then passing the oil-sodium mixture through a colloid mill, or other apparatus capable of breaking the molten metallic sodium into colloidal or quasicolloidal form, and dispersing it throughout the oil. After passing through the colloid mill, the oil, which now contains the sodium in colloidal or quasi-colloidal form,.is passed through a heater wherein it is heated to the temperatureat which it is desired to have the reaction take place. This temperature is usually in the neighborhood of 450 F. Within the reaction chamber the oilsodium mixture is maintained in a 4constant state of agitation, the length of time for treatment being varied according to the type of oil being treated, and also according to the purity of the oil being treated. After the oil-sodium mixture has remained in the reaction chamber for a suiiicient length of time to insure completion of the reaction, the mixture is drained from the chamber and passed either to a. devicer for coagulating the unreacted sodium which is in colloidal form or through a. cooler and then to aA lter press for separation of unreacted sodium and sludge produced from the oil. The sludge is then passed to a further stage in the process wherein the unreacted sodium may be removed therefrom; as will hereinafter be more completely described. With some oils having a high degree of purity the reaction chamber may be dispensed with, as suiiicient contact is obtained during the passage `of the oil-sodium mixture through the colloid mill.

The sodium apparently acts as an inductor or promoter for the reaction rather than a catalyst.' The reaction is in the nature of a polymerization and/or dehydrogenation of the unsaturated portions of the oil, reducing them toa form inwhich they may be removed from the oil by iiltraton or other means. Certain sulphur compounds in the oil, and of course any water present, will react with a very small proportion of the sodium before the sodium begins its role as inductor or promoter. However, this phase of the treatment'is not novel per se, as the desulphurization and dehydration of cils by the use of very small amounts l of sodium is old, as heretofore set forth. It is generally recognized that the degree of concentration of a catalyst in a reactionrmixture does not affect the reaction and that inductors or promoters do affect a reaction mixture by their degree of concentration. Since, therefore, it has been observed that small amounts of sodium do not promote the desired reaction in the oil, it is believed that the conclusion above referred to is correct, namely, that the sodium, after it acts as a direct desulphurization or dehydration reagent, becomes a promoter or inductor for th dehydrogenation reaction.

It is necessary, in order to secure substantial dehydrogenation, that the sodium shall be in colloidal or quasi-colloidal suspension in the oil. It

is also admissible, if not necessary, in order to secure the maximum desired dehydrogenation, to use not less than from 170 to 220 grams of sodium per liter of oil, dependent on the oil being treated. It is also necessary to use this minimum proportion of sodium if it be desired to recover anything approaching a quantitative recovery ol sodium. As the quantity of sodium is reduced, the proportion possible to recover is reduced. Metallic sodium being comparatively expensive, as compared, for example, with reagents such as sodium hydroxide, its recovery is essential to an economical practice of the process. For the reasons stated, it is desirable, if not necessary, to use a larger proportion of sodium than has hereto fore been utilized, as well as to use it in colloidal form.

Alloys such as sodium-potassium, sodium-calcium, sodium-barium, sodium-tin, sodium-lead, and sodium-ammonium may be used in the process instead of pure sodium. Sodium amalgam may also be used. It is only necessary to carry out the reaction at temperatures above the melting point of the alloy or amalgam, and reduce the amalgam to colloidal or quasi-colloidal form. It is of course known that ammonia when in combination with sodium acts as a metal, the combination being, to all intents and purposes, an alloy.

A better understanding of practicable process for producing my improved lubricating oil may be had by reference to the accompanying draw- The oil is removed through line Il, and forced by means of pump I2 through heater I3 to colloid mill I4. Before entering the colloid mill, there is added, to the oil stream in pipe I I, a predetermined amount of molten sodium from line l5, which is in communication with a molten sodium storage vessel I6. On passing through the colloid mill, the sodium and oil are thoroughly mixed, and the molten sodium is reduced to an extremelynely divided condition.

Leading from the colloid mill I4 is line Il, in which is placed heater I8 for heating the oil-sodium mixture. This line I1 leads to an agitator I9 having therein a motor driven centrifugal agitating member 20. There may be provided three or more agitators such as I9 in order, if desired, to make the process a continuous one. The centrifugal agitating member 20 is rotated at an extrcmely high speed of the order of 9000 R. P. M. The agitating member itself consists of a disc having a number -of radial passages therethrough, and a. downwardly extending portion having a passage therethrough which communicates with the radial passages in the disc. By rotating the agitating member at high speeds, the oil-sodium mixture is drawn through the downwardly extending portion and is expelled through the radial passages by the centrifugal force created by the high rotative speed. 'Ihe agitator I9 is provided with suitable heating means (not shown), to maintain the oil-sodium mixture at reaction temperature during its entire time of treatment. Any suitable heating means may be used, such as electrical resistance heaters or heating coils employing steam or hot oil.

It ispracticable, in place of the specific agitator described, to employ agitators of other types commonly used in the treatment of oils. Indeed it may be possible, after the passage through the colloid mill, to dispense with agitation, since agitation is not required to maintain the sodium in suspension in the oil. Agitation, however, is desirable, if not required, to maintain the entire body of oil at a substantially uniform temperature. It is also possible, with the type of agitator shown, to add the oil and molten sodium directly and reduce the sodium to colloidal form by the action of the agitator alone. This procedure, however, consumes considerably more time than does the combination of the colloid mill and agitator.

-From the bottom of the agitator I9 a valve line 2| leads to a tower 22. The treated mixture of oil, sludge and unreacted sodium is forced by means of pump 23 in line 2| into the tower 22. This tower 22 contains packing material 23, which may be iron Raschig or Lessing rings, filling the tower to approximately two-thirds of its capacity,

The cil, containing sludge and some sodium, drains from the bottom of the tower 22, through line 24, containing pump 25, and cooling coils 26, to a filter press 21. 'I'here may be provided a number of presses in order that the process may be carried on continuously. Line 28 containing pump 29 leads from a filter press 21 to storage tank 30 for finished oil. The sludge, togetherl with the nely divided sodium, forms filter cakes on the filtering media within the press 2l.

Leading from the top of tower 22 is a line 3I for the removal o'f .hydrogen which is formed during the treating step and is adsorbed by the sodium.

From a point below the top of tower 22 there '15 extends a line 33 containing pump 34 for drawing oi .metallic sodium which is separated in .the tower and accumulates to the level of line 33. This metallic sodium is passed to a Washing tank 35, wherein it is mixed with naphtha entering through line 36. The mixture of naphtha and sodium is withdrawn from the top of the washing apparatus through line 31 containing pump 38. The naphtha-sodium mixture is thus pumped to a settling chamber 39, wherein the sodium is settled from the naphtha and is pumped out through line 40 by means of pump 4I and returned to sodium storage receptacle I6.

and therein admixed with molten sodium admitted through line 53. After being .thoroughly ground with molten sodium, the mixture is passed through line by means of pump 46, and is forced through lter press 41. The ltering medium in press 41 is of a type which will be wetted by metallic sodium and will therefore permit the free coalesced metallic sodium to pass through, Vbut will hold back the sludge, which collects on such filtering medium as a lter cake. The sodium which has passed through the press 41 is removed through line 48 and part of it is forced, by means of pump 49, to the sodium washing chamber 35, and the remaining portion is recycled through line 53 to the ball mill 44 for admixture with sodium-containing sludge removed from press 21. When lter cakes of the desired depth have been formed on the media. in press 41, they are removed therefrom.

In operation, the oil removed from tank I0, containing the charging stock, is heated in heater I3 to a temperature somewhat above the melting point of metallic sodium (207 F.), and is then passed through line I5 leading to the colloid mill. Line I5, as heretofore explained, conveys molten metallic sodium from the storage receptacle I6 to the colloid mill. The sodium and Ioil are so proportioned that the charge entering colloid mill I4 is '10 pounds of sodium to 1 barrel of. oil (equivalent to approximately 200 grams of sodium to 1 liter of oil). through the colloid mill the-sodium is reduced to an extremely nely divided state and thoroughly admixed with the oil. The oil-sodium mixture leaving the colloid mill is then passed through heater I8 wherein it is heated to a temperature within the range of 400450 F. Enough oilsodium mixture is f ed to the agitator I9 to fill it to approximately two-thirds of its total capacity. Due to the high rotative speed of the agitating member 20, the oil-sodiumY mixture is maintained in a state of agitation insuring equal temperature conditions throughout the whole mixture. 'I'he oil-sodium mixture is maintained in the highly agitated condition for a period of time ranging from half an hour to thirty-six hours, depending upon the type of oil being treated and the resistance to oxidation or change in temperature-viscosity relationship desired.

Exactly what chemical change takes place in the oil is not known, as the sludge which is re- In passing covered has so far resisted all attempts at analysis. However, it has been determined that both dehydrogenation and probably hydrogenation are effected by the sodium treatment. That dehydrogenation is effected is shown by the presence of adsorbed hydrogen in the unreacted sodium. That hydrogenation is effected may be inferred by the change in temperature-viscosity characteristics and the change in specii'lc gravity. The presence of free hydrogen in an adsorbed condition in the unreacted sodium present in the sludge was rst detected V.,vvhen analyzing the sludge to determine the amount of sodium which had been reacted. This analysis was carried out 1 by adding alcohol to a weighedsample and determining the amount of hydrogen evolved.

Since the amounts of hydrogen evolved were greater than the equivalent of the amount of sodium which was known to be present, it was apparent that free hydrogen must be present. This was also conclusively demonstrated when the sludge was later treated with a further excess of molten sodium, and then washed with naphtha. Since no chemical change was apparent in the naphtha or in the sodium, and since free hydrogen was evolved, there can be no doubt that a dehydrogenation of the original oil took place in the agitator. Since the temperature-viscosity characteristics and the gravity of the oil were also changed, it was evident that dehydrogenation and possibly hydrogenation of the original oil had been effected. It ,is well known that naphthenic base oils have a temperature-viscosity slope differing from the temperature-viscosity slope of paramn base oils, and when the temperature-viscosity slopes of the untreated and the treated oils were compared, itl

Was found that the treated oil more nearly approximated the temperature-viscosity slope of a paran base oil. This fact, coupled with the change in specic gravity, corresponding to increase in the percentage of hydrogen in the oil, leaves no doubt as to the occurrence' of dehydrogenation and possibly hydrogenation. It is, of course, evident that if unsaturated components of the original oil are dehydrogenated by the action of the sodium and the dehydrogenated components are removed as sludge, the remaining components of the oil will be substantially saturated. It is also evident that the sodium treatment may dehydrogenate a portion ,of the unsaturates and hydrogenate the remaining unsaturates. There is concrete evidence of the dehydrogenation and removal of vunsaturates but no irrefutable evidence of hydrogenation of a. portion of the unsaturates.

The treated cil, containing unreacted sodium and sludge, is drained from the agitator I9 and pumped into the top of packed tower 22, which contains-in addition to the packing, fresh molten sodium. The entering mixture may be considered as an oil-sodium emulsion with the oil in the external continuous phase. Obviously, with such an emulsion, the coalescence of the sodium particles is impossible until the phase is changed and the sodium becomes the external continuous phase, or interlacing phase. This change is accomplished byowing the oil, sludge and sodium mixture downwardly through the tower 22 which contains Raschig or Lessing ring packing and metallic sodium. In flowing down'through the tower, the oil sodium emulsion changes phase and the sodium in the emulsion becomes the external phase, due to the action of the large bath of sodium in the tower, which coalesces the finely divided sodium that mixes with the sodium constituting the bath. In practice, all but about 1'1 or 18 per cent of the unreacted sodium will be recovered in the tower 22. When rening some light oils, the oil-sodium-rnixture may have a speciiic gravity less than that of the molten sodium at the temperature existent in tower 22. In such case the oil-sludge mixture would be admitted to the bottom of tower 22 and ilowed upwardly through the sodium. The sodium freey oil-sludge mixture would then be withdrawn from tower 22 near the top thereof, and the excess sodium at a point below that at which the oil sludge mixture is withdrawn.

The oil-sludge mixture, still containing a small proportion of unreacted sodium, is passed i'romv the bottom of the tower vthrough cooling coils- 25 to the lter press 21. Due to the coalescence in the tower of the finely divided sodium present in the oil-sludge mixture, the amount of freeA sodium in the tower is increased, the excess being drawn oi through line 33 and passed to the washing chamber 35.

In some cases it may be desired to eliminate the sodium recovery step in tower 22, in which case the oil-sodium mixture from agitator I9 will be passed directly to pump 25, cooler 26, and press 21 by by-pass 56 shown in dotted lines.

As hereinbefore explained, the oil sludge mixture after being cooled in coils 26 to a tempera- .ture approximating 70 F., is passed through the filter press 21, wherein the oil is separated entirely from sludge and unreacted sodium and is passed out through line 28 to storage tank 30. From time to time the filtering media in press 21 are removed and the sludge cakes accumulated thereon are placed in ball mill M, and ground with molten metallic sodium. When this grinding is complete, the sludge-sodium mixture is subjected to further pressing in filter press 41. This operation results in the removal of all unreacted sodium from the sludge. The free sodium is then partly recycled to the grinding operation in mill 44, and partly pumped to washing tank 35.

The washing and settling operations remove from the sodium the hydrogen which has been adsorbed therein. In the washing step, carried out in tank 35, a small amount of hydrogen may be released, which is from time to time vented through line 50 to line 3i. The naphtha used for washing the sodium to remove adsorbed hydrogen is circulated continuously through the tanks 35 to 39, and is unchanged by the operations performed therein. The sodium is removed from settling tank 39 and is pumped to sodium storage tank I6. Sodium, to make-up for that lost in the reaction, is added to storage tank IB and may be added in the molten state through line 5I It is to be understood that any low boiling metal may be used to dissolve the unreacted colloidal sodium, or mercury may be used to form a sodium amalgam which can be readily removed from the treated oil or sludge. Such metals as potassium, calcium, barium, tin and lead may be used to coalesce the colloidal sodium and would be equivalent to sodium used for the same purpose.

In all steps from its admission with the oil to the colloid mill to the iinal removal of all unreacted sodium, except in the step of separating the oil, the sodiumv is maintained in a molten condition.4 The temperature in agitator I9 is substantially 450 F. A like temperature prevails in tower 22.

Other methods of treatment with and recovery of metallic sodium are described and claimed in my prior co-pending application Serial No. 685,994, iiled August 21, 1933, but are not described herein as such further description would be superfluous.

Washing apparatus 35 and settling apparatus 39 are also maintained at temperatures above the melting point of sodium. The sodium which is separated with the sludge in lter press 21 has been cooled to a point below its melting point, but is subsequently heated by the addition of molten sodium to ball mill M. Since the only sodium which circulates through ball mill 44 is that which is-recovered, there is provided, preferably in line I8, a heating apparatus 52, to which heat may be supplied, preferably by means of superheated steam circulated through the coil therein, although mineral oil may be used as the heat transmitting medium. Since the melting point of sodium is below the boiling point of water, the handling of molten metallic sodium presents no diiiiculties whatever. It is, of course,

understood that all sodium-carrying lines should be insulated.

The operations so far described have been directed to procedure for treating oil with sodium by a batch process. It is to be understood, however, that the treating and recovery methods hereinbefore described may be carried out in a continuous manner. For instance, oil and sodium in the proper proportions may be charged to agitator I9, (Fig. 1) and the mixture agitated until a sample of the oil upon withdrawal shows that it has reached the degree of purity or dehydrogenation desired. When the oil has reached such a state, fresh oil-sodium mixture is continuously charged to the agitator I9 at a slow rate and treated oil-sludge mixture is continuously withdrawn from the agitator at the same rate that the untreated oil-sodium mixture` is charged. The treated oil-sludge mixture is then continuously passed through the tower 22 to coalesce most of the sodium contained in the sludge, and the largely sodium free mixture is withdrawn from tower 22 and passed through lter press 21. 'I'here will, of course, be provided a number of filter presses such as presses 21 and 41, and also several grinding devices, such as ball mill 44, in order that the final recovery of sodium from sludge may be continuous.

Numerous variations of the described preferred process are practicable. For instance, the` oil treated may be a distilled lubricating fraction whichhas or has not been acid treated or subjected to other refining processes such as SO2 treatment or contact clay treatment, or the oil treated may be a residual lubricating oil which has or has notv been subjected to the usual refining steps. The third modification, and probably the most desirable, is the treatment of a reduced crude before distilling into the various desired lubricating fractions. If it is desired to treat a reduced crude, the fractions including ali` or light gas oil and all lighter fractions are removed by overhead distillation in any known manner, and the reduced crude or mazoot is treated as herelnbefore described by the addition of an excess of .metallic sodium to the mazoot. 'I'he mixture is then subjected to the heating and reclaiming steps herein described` It has been stated that this modification is probably the most desirable, since the treating time is greatly 4lowered. For instance, with some impure lubricating oil fractions, the time of reaction may be as high as 36 hours, but when treating a mazoot with sodium the reaction time is out to one-half an 110111'. I pil. 1V

The following speelde-examples will serve to (distlllate) illustrate the oil obtained when treating disi tillates and when treating reduced crudes and gimp- Of treatment' F 430440 5 ime of treatmc t hours.` then distilling lthe desired lubricating fraction gem ogtratiq F f .l 2?

rams 0 apel 1 GIO 0l herefrom' Yield of refined oil percent 75, 7 Yield of polymer (by diierence), percent 24. 3 (.311.) ...33.11. 10 s a e 1S ate Before After lo B f B i Characteristics ofthe oil refining renmg e Ol E 0r6 After Na After Na N tre t- Nat e tainga "etmg inrga tfeetlng Gravity. A. P. i is. 5 23. 2 glash, Cleveland open cup ll'e Gravi A. P. I 21.1 24.1 10.7 23.2 Vis. S- U- at 100 F-. 6113 2219 l5 F1555,ty cleveland open gis. 0% ig 73g l5 D Fi'fs': i?? csibrfNiia. A jj 5% i2 Viscosity, s. U./100 152 144 533 440 Pour restyli- S- T- M., +25 +5 Viscosity, s. U./130 70 79 209 179 Denlulslbllltrm 18 1020 Viscosity, s. U./210 F 39 43 54 54 Emulsibihty 20c. Cuff Good 2o golortt. A l 13- 2% 11-5 ggiliradson carbon, percent T0. ce TO 20 0111' es i 5 5 0 T ra r Demulsibility. 1260 1620 1620 1620 Rawtioi'i...T Neutral Neutral Emulsibility Good Good Good Good Sligh oxidation.. 65.6 0. 0 Steam emulsion- Sulphur, percent 0. 45 0. 03

The following examples will serve as illustra- Tplrstire of treat- 41H40 41H40 tions of the oils produced when mazoots or topped Yield f1-35124555535.' crudes (free of gas oil and lighter fractions) are Glis-f'-s-i- 85 90 treated with colloidal metallic sodium, and then pei-liter ofoii 200 200 distilled under vacuum into cuts suitable for use so as commercial lube oi1s:

Oil V-Mazoot from spindle top crude Oil IH Oil VI-Mixture consisting of mazoots from: (distillate) 25% Esperson crude, 4 25% Vinton and Goose Creek crudes, and 35 Temp. of treatment 42o-440 50 Liberi; crude,

Time of treatment, ours 20 y Temp. of filtration, F 70 333333335 le 0 fe e 0 ,peln Yield of polymer", percent... 17. 5 011 V 011 VI Before After re odium/igitl ratio usetd 2ggallwliter oil... ig() g. S/liter oil. ernp.0 reatmen 4 5-45 1. Charactenstlcs of the m1 l'emng fllllng Time of trentment 1 hour. l hour.

. Temp. of iiltration 70 F 70 F. Gravity A P I 18 3 22 1 Apparatus used Celntgugl CeIBt-(iigalz zizflgaitoltir Flh: Cleveland open cup' oF 450 430 i Suction -lter, S'Lction fil-ter.. gesayboltwv 8.100. F 1,3 5gg Yrs/1d og lfva treat. 81.0% 73.0%. 45

vis. saybolt Univl at 130: 2-.- 672 461 egg/[M222 un' 2375-0 81?? EN at 210 3g 18g Amounn i sodium 2.7% 0.36%. 1 0011511 e :gglggi- S- T- M F 162g Hydrogglgas formed' 163.0 cu. ft 83.5 cu. it. nmoisibii1y `2 21 Good Good lI/zootj mmm Y 5o Comdson Wbonr pement 0- 22 0 06 Hydrogen gas formed 201.2 cu. It 114. 4 cu. ft.

-sh L. Nlftar Nlrtca por bbl; Na treat. l Sli hnrifinn 4&1 0.0 Mazoot. Supliui-,pei-cent 0.35 0.02

*H7 at 70 F. and 14.7 pounds pressure. 55 Dstllates from oil V after treatment Temp., F. Viscosity, F. Per- Porcent Per- 60 Mm. cent A. P. I. Flash, Eire, Sligh Color COIL cent Neut No pres. chg grav. F. F. oxid. N. P. A. can Suu. 4 Vap. Liq'. 100 130 160 210 bon orig. oiiv 20.3 350 410 934 1. 35 0.34 2.0mg-K0151.v Na created ouv 23.9 355 400 452 0.o 5% 0.16 0.09 Neut. 65

\ out L.-- 328 426 2 10 27.0 205 235 4s 0.0 1- 0.01 0.04 Do. 350 460 2 10 25.5 320 350 3s 0.0 i- 0.01 0.03 Do. 388 492 2 10 25.0 350 405 135 0.0 1- 0.01 0.04 Do. 414 522 2 10 24.0 395 440 265 `0.o 1- 0.01 0. 04 Do. 435 540 2 10 23.5 410 470 513 0.0 1 0.01 0.06 Do. 5---- 400 575 2 10 22.3 440 510 803 0.0 1% 0.01 0.05 Do. 7.-.. 434 009 2 i0 22.7 455 530 1130 0.0 1% 0. 01 0.04 Do. 70

33 i v3 33 23 33 33 33 33 3- 1 M 4- 0. 619 73s 1 3 24.1 545 525 2215 0.0 3| 0.11 0.05 Do.

mms 7 22.5 655 725 3.8 Dk. red 1.79 0.09 Do.

Distillates from oil VI after treatment Temp., F. P ViSeOSitYi F Perg P 8l'- cen el'- Mm. cent A. P. I Flash, `1:;11'0, Sl1 gh Color Con cent Neut No. pres. ch mv. F. F. oxid. P. A. car. sul! Vap. Liq. 3' 100 130 150 210 bon Orig. o] VI- 19.3 ZIO 325 901 2.75 0.38 23mg. KOH Na mated oil 24.4 285 320 348 0.0 3 0.11 0.08 eut.

cui 1 300 355 1 l1o 29.8 210 240 41.2 0.0 1- 0.01 0.04 D5. 2 345 358 1 10 25.8 270 295 55.4 0.0 1- 0.01 0.04 D5. 352 420 1 10 25.5 310 345 so 0.0 1- 0. 01 0.02 D5. 417 455 1 10 24.4 350 400 185 0.0 1 0. 01 0.04 D0. 445 495 1 10 23.4 aso 440 380 0.0 1;/ 0.01 0.02 D5. 475 532 1 10 22.4 405 480 79s 283 00 0.0 152 0. 01 0.04 Do. 517 582 1 10 21.7 400 525 1505 500 80 0.0 114+ 0.01 0.02 D0. 555 548 1 10 221 505 500 024 287 10o 0.0 2+ 0.08 0.04 D5. 9..-- 523 732 1 10 227 550 515 1001 427 138 0.0 3+ 0.21 0.00 Do.

Bumm- 10 221 555 715 177s 455 1.5 Dk. red 1.57 0.05 Do.

Vacuum distillation of 8th distillate from oil VI Vacuum distillation of 8th distillate from oil V Y Temp., F. u Cut Pres. Chg. gli@ s1/10 Color Temp., F. 0 Vap. Liq. out Pres. chg. Falh' El?) Visi/2 1 0515i Vap. Liq. Per- Mm. cent 514 552 1 10 470 540 s4 1%- Mm 2t 2li i 13 it 32 i5 1 484 520 1 10 440 526 79 1555 54s 508 1 10 485 570 95 1+ 489 52s 1 10 450 540 s2 1 1+ 555 503 1 10 500 585 99 M+ 495 536 1 10 470 545 83 1% 555 605 1 10 505 590 102 154+ 505 542 1 10 470 550 83 1 552 51s 1 10 510 595 105 2+ ggg g gg w 45 580 532 1 1g 540 605 111 2% 233? ggg g gg gg() 1 i 620 v550 1 550 030 123 2%- 5 1 54a 589 1 10 505 585 85 192 lo 575 650 169 5% S 1 53 15 101 Vacuum distillation of :mi distillate from oil v1 Vaeiiii il' lillatioii' 9m a' lill l rom 'l v Temp" F' m w of u a 6 f m Cut Pres. Chg Fgl Elise] VSgm Color Vap. Liq.

Temp., F. Per- Flash Fire Vis/210 M nt C t i m. ce

u- Pres Chg F Ff F. 00x 55a 530 1 10 500 505 114 215+ Van Liq- 557 540 1 10 505 500 114 2%- 580 550 1 10 525 510 121 214+ 590 001 1 10 530 520 121 214+ P"- 502 572 1 10 540 530 120 2m- Mm nl 010 581 1 10 545 535 136 2%- 602 1 10 480 600 82.2 1V 52a 595 1 10 550 540 143 3- 509 1 1o 500 580 89.2 1'. 534 711 1 10 555 550 152 3% 617 1 10 510 595 921 1% 552 725 1 10 555 555 172 3%- 32 l 13 :2 5: 1%

5 1 k 554 1 10 530 520 90.4 15: lo 620 695 248 B 070 1 10 540 530 105.9 2 ggg 18 555 535 1112 2V 5 5 1237 2 It will be understood that the values given in 510 575 177.2 Derk the tables and in the appended claims refer, un-

ed less otherwise specically noted, to the results of Vacuum distillation of 10th distillate from oil V Temp.,F. Cut Pres. Chg 1281511 Eig' vwl/210 Color vap. Liq.

Per- Mm. cent 624 1 10 480 555 83 316+ 628 1 l0 545 635 107 3- 637 1 10 555 635 116 2%- 648 1 10 555 635 118 2 660 l 10 560 645 126 2 672 1 10 570 650 128 2 677 1 10 575 650 135 2 692 1 10' 585 665 141 2%- 7Hl 1 10 615 685 158 3% 10 630 700 229 Dark red tests approved by the American Society for Testing Materials.

Where, in the tables, the values for sulphur content and Conradson carbon are given in terms of percentages, it will be understood that such percentages are approximate, in that they are expressed as accurately as possible, where the percentages are expressed in terms of hundredths of one per cent. Thus, in the tables entitled Distillates from Oils V and VI after Treatment, the Conradson carbon of a number of cuts is substantially less than the .01% specied, but is expressed by that percentage merely to indicate that the Conradson carbon content is not absolutely zero.

While, in the examples given in the tables entitled Distillates from Oils V and VI, the sodium treated long residua or mazoots from which the oils are distilled have respectively Conradson carbon contents of .16% and .11%','other sodium '5 treated long residua may have Conradson carbon contents varying from .05% to .3%.

What I claim and desire to protect by Letters Patent is as follows:

1. A residual petroleum oil produced by distilling from the crude gas oil and lighter constituents and which contains and from which can be produced a substantially full range of lubricating oil constituents varying from a distillate having a flash point not over 300 F. and a fire point not over 350 F. to a distillate having a flash point not less than 525 F. and a fire point not less than 600 F., characterized by the fact that its organic acidity as tested by the A. S. T. M. method does not exceed two-hundredths neutralization number, its Conradson carbon content is less than four-tenths of one per cent. and its Sligh oxidation test is zero,

2. A residual petroleum oil produced by distilling from the crude gas oil and lighter constituents and which contains and from which can be produced a substantially full range of lubricating oil constituents varying from a distillate having a ash point not over 300 F. and a reA point not over 50 F. to a distillate having a flash point not less than 525 F. and a fire point not less than 600 F., characterized by the fact that its organic acidity as tested by the A. S. T. M. method does not exceed two-.hundredths neutralization number, its Conradson carbon content is less than one-fourth of one per cent and its Sligh oxidation test is zero.

3. A residual petroleum oil produced by distilling from the crude gas oil and lighter constituents and which contains and from which can be produced a substantially full range of lubrieating oil constituents Varying from a distillate having a ash point not over 300 F. and a. re point not over 350 F. to a distillate having a flash point not less than 525 F. and a fire point not less than 600 F., characterized by the fact that its organic acidity as tested by the A. method does not exceed two-hundredths neutralization number, and its Sligh` oxidation test is zero and Whose highest distillable lubricating oil portion has a Conradson carbon content less than four-tenths of one per cent.

Si 'I2-M.`

' characteristics specied in claim 2- 4. An improvement in lubricating oils which are distillates of naphthenic base petroleum oils and which have flash points ranging from 210 to 550 F. and higher re points ranging from 240 to 625 F. and Whose organic acidity as tested by the A. S. T. M. method does not exceed .02 neutralization number, characterized by the fact that its Conradson carbon content ranges from.

about one one-hundredth of one per cent with oils in the low part of the range to less than .24 per cent with oils at the highest part 'of the range, that its color number ranges from less than one N.- P. A. in the low part of the range to less than 4 N. P. A. in the highest part of the range, and that its Sligh oxidation is zero.

5. Animprovement in lubricating oils which are distillates of naphthenic base petroleum oils and which have flash points within the range 210 to 460 F. and higher re points within the range 240 to 530 F., and Whose organic acidity as tested by the A. S. T. M. method does not exceed .02 -neutralization number, characterized by the fact that its Conradson carbon content is less than one-fortieth of one per cent, that its color number is not over 2 N. P. A., and that its Sligh oxidation is zero.

6. An improvement in lubricating oils which are distillates of naphthenic base petroleum cils and which have flash points Within the range 450 to 550 F. and higher fire points Within the range 520 to 625 F. and whose organic acidity as tested by the A. S. T. M. method does not exceed .02 neutralization number, characterized by the fact that its Conradson carbon content is less than one-fourth of one per cent, that its color numberis not over 4 N. P. A., and that it Sligh oxidation is zero.

7.'A residual naphthenic base petroleum oil produced as dened in claim 1 and having the characteristics specied in claim 1.

8. A residual naphthenic base petroleum oil produced as defined in claim 2 and havi g the 9. A residual naphthenic base petroleum oil produced as dened in claim 3 and having the characteristics specied in claim 3.

RICHARD S. VOSE. 

